Difuryl sulphonates



Patented Apr. 10, 1945 DIFURYL SULPHONATES Jack T. Thurston, Riverside, Com, assignor to American Cyanamid Company, New York, N. Y., a corporation of Maine No Drawing. Application August Serial No. 458,278

3 Claims. (01. 260-845) This invention relates to certain new and useful compounds and to their preparation More particularly my invention relates to difuryl substituted organic sulphonates.

An object of this invention is to provide sulphonates which contain two furyl groups as substituents.

Another object of this invention is to provide difuryl substituted organic disulphonates.

Still another object of my invention is to pro-: vide organic sulphonates suitable for the preparation of resins having cation active properties.

A further object of my invention is to provide processes for preparing sulphonates of the aforementioned type.

The compounds which form the subject of this invention have the following general formula:

' Il...:. i x;.... lj

and where M is a metal, or hydrogen, or

'-H-NR:R:R4

filmiilmfj where R and R are the same as above with a bisuiphite or with sulphur dioxide, preferably in a suitable medium such as water. Compounds of the formula:

[Letting may be prepared by condensing furfural with a ketone containing active methyl or active methylene groups.

The following examples, in which the proportions are in part by weight, except as otherwise indicated, are given by way of illustration and not in limitation.

Exams: 1

Preparation of disodium 1,5-di-alpha-juryl-3- ketopentane d suIphonate-L-S Parts Difurfurylidene acetone 86 Sodium bisulphite 83 Water 118 These substances are heated to boiling and refluxed in a suitable apparatus for about 16 hours.

The resulting solution is treated with decolorizing charcoal and filtered. The product is precipitated from the filtrate by addition of the ethanol. A yield of about 84% is obtained. The product does not melt at temperatures up to about 250 C.

EXAMPLE 2 Preparation of 2,6-bis- (alpha-furyl-potasslumsulphomethyl) -cyclohexanone Parts Difurfurylidene-cyclohexanone (0.54 mol) 13? Potassium metabisulphite (0.54 mol) Water 280 The monoethyl ether of ethylene glycol 325 eration the reaction mixture is cooled thereby causing a large mass of crystals to separate. The solid material is filtered, suspended in the monoethylene ether of ethylene glycol, filtered, washed with an additional quantity of said ether, washed with acetone and dried. An additional quantity of the product may be obtained by adding about 2 volumes of acetone to the ether filtrate thereby precipitating crystals which are filtered, washed and dried. The combined yield of the product is about 91% of the theoretical and it melts at about 250 C. The product shows the following analysis:

Per cent Percent Per cent Calculated f0! cnnulhsgxg g 69 3. 24 12. 96 .69 s. a5 13. 15 ohm! 38.61 3.34 13.07

. after crystallization from aqueous butylhetone,

Preparation of furlurylidene-methvl-a-lurfumudene-ethyl ketone Parts Methyl ethyl ketone mols) 360 Sodium hydroxide (2.2 mols) 86.5 Alcohol 1,000 I 'urfm'al (11 mols) 1,110

A mixture of the ketone and a solution or the sodium hydroxide in the water is placed in a reaction 'vessel provided with a mechanical agitator. The alcohol is added to give a clear solution after which the iuriural is added slowly over a period 01 about 1 hour. During the addition of the iuriural, the temperature rises to about 62 C. and the color becomes dark. The reacting mixture is agitated for about 5..hours and then permitted to stand for about 16 hours after which time the'product has crystallized as a dark mass of solid material. This mass of material is broken up and washed with cold methanol. Alter drying the crystals a yield of about 65% of the theoretical-is obtained. The crystals arelight yellow having a melting point of. 60-61 C. and alcohol show .the following analysis:

Percent Percent o n Oslculatedior CuHuOg rats is 0W1 as is Exams: 4 0 Preparation of Miami-methyl furjuml-ethyl I ketone disulphonate Parts Furiurylidene methyl furiurylidene ethyl ketone (2 mols) 461 Potassium metabisulphite (2 mols). 449 Water 800 A mixture of these substances is refluxed in a suitable reaction vessel for about 1 hour and then maintained at approximately 85 C. for approxi- -mately 16 hours. A white crystalline solid deposits on cooling. The solid material is filtered and washed with acetone. The filtrate is poured into twice its volume oi ethanol, thereby precipitating an additional quantity oi the crystalline material. This material is washed with acetone and combined with the other crystals and dried at about 120' C. A yield of about 83% of the theoretical is obtained. The product does not melt at temperatures up to about 200 C.

In order to obtain the sulphonate contemplated by my invention it is apparent fromthe i'oregoins examples that a total cl 2 mols iuri'ural with 1 mol of a ketone having two active groups either methyl or methylene, and resultin'gcompoundinturnmaybereactedwithi or 2 mole of a bisulflte or sulphurous acid. It may be desirable to employ anexcess oi the bisulilte order to drive or o! the i'uriurylldene ketone in the reaction to completion. I

Other ketones having active methyl or active methylene groups may be reacted with rurfural and converted to the sulionate in accordance with Y the ioregoing disclosure. Thus, for example other ketones such as methyl hexyl ketone, di-nbutyl ketone, methyl-n-propyl ketone, methyl-ncycloh'exanone, cyclopenchem formula:

a o a met-Lbs; o 0

may be converted to the corresponding sulphonate by treatment with a bisulphite or with sulphur dioxide in a suitable ,medium such as water. Examples of suitable bisulphites include sodium bisulphite. potassium bisulphite, ammonium bisulphite or other desirable metal bisulphites such ascalcium bisulphite. In general. the alkali metal bisulphites' are prei'erred. The hydrogen sulphonate may be converted into the corresponding metal, ammonium or amine salts if desired. Examples of amines ior such salts are: methyl amine, dimethyl amine, triethyl amine, pyridine, the mono-, di and tri-ethanolamines, etc. Another method of producing sulphonates is by treatment of the iuriurylidene compounds with a hydrogen halide followed by treatment with sodium sulphite or with other alkali metal sulphites. Thus, for example, hydrogen chloride may be added to iuriurylidene acetone and the resulting material treated with sodium sulphite. Still another type of sulphonate may be prepared by the condensation of iuriural with a halosen so submitted ketone such as chloroacetone followed by treatment (1) with a hydrogen halide and then with a sulphite or (2) with a mixture or abisulphite and a sulphite preferably in a molar ratio 01 about 2:1. The bisulphite or sulphite- 5 may be a salt of an alkali metal, ammonia, or any other desired metal or amine.

The sulphonates may be prepared from the furrurylidene compounds by reaction with bisulphites tion is preferably, carried out under pressure,

e. g., 25-100 pounds per square inch and/or at relativelylow temperature such as about 20 C. The time 01' reaction varies somewhat according to the compatibility otth'e reactants. Thus.

it a homogeneous solution of the reactants be emplayed, the reaction will usually be completed in irom about ,6 hour to about 2 hours. On the other hand, it the solution 01 the reactants is not homogeneous 6-8 hours oreven more may be I required. Generally water is employed as the solvent medium for the bisulphite and 'iuriuryli-v dene compound, but it suflicient solubility i not obtainedother solvents may be used. Mixtures oi water and water miscible organic solvents are so especially suitable since the water i a good solvent for the sulphite while the organic solvent is a good solvent for the iuriurylidene compound. Examples oi suitable solvents are: methanol. ethanol, propanol, isopropanol, butanol, dioxane, 06 the lower alkyl monoethers of ethylene glycol and diethylene elycol, such as the monoethyl ether of ethylene glycol, the monobutyl ether of diethylene glycol, etc. Furthermore. inert ketones may be used as solvents in the production or sub 7 phonates. In some instances it may be desirable to employ active ketones as intermediates in the preparation of sulphonates. Thu the bisulphite may be added to amactive ketone and'this in turn react with the rurturylidene compounds, the

u iormergivingupthebisulphitetothelatter.

My i'uryl substituted sulphonic acids are espeand scope or the invention defined in the anciaily suitable for resiniflcation with an aldehyde pended claims.

' to produce resinous materials having cation active I claim:

perties. They are also useml in the prepua- 1. A di-alpha-turyl ketone disulp te. 11 of emulsifiers, wetting agents, dispersing 2. lj-di-alpha-i'uryl-B-ketopentane disulphoazents and as intermediates in the synthesi of note-1,5. V many organic compounds. 7 v3. A 2,8-bis(alpha-i'uryl metal sulphomethvl) Obviously many modification and variations in cycloheunone. the p and compositions described above i JACK '1. THURSTON. may be made without departing'from the spirit 1o cEfimFicATE' OF GORRECTION. Patent'No. 2, 7 ,152; .April 10, 191

JACK r. msron.

It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction as followst Page 2, sec- .ond column, line 50, for the word "sub1nitted" read --substituted-; page 5, first column, line 7, after "many" insert -.-other--; and' that the said Letters Patent sheuldbe read with this correction thereinthat the same inlay conform to the record of the case in the Patent Office- Signed and sealed this 26th day of June, A. 1:. 1915.

. Leslie Frazer (Seal) Acting" Commissioner of Patents.

My i'uryl substituted sulphonic acids are espeand scope or the invention defined in the anciaily suitable for resiniflcation with an aldehyde pended claims.

' to produce resinous materials having cation active I claim:

perties. They are also useml in the prepera- 1. A di-alpha-turyl ketone disulp te. 11 of emulsifiers, wetting agents, dispersing 2. lj-di-alpha-i'uryl-B-ketopentane disulphoazents and as intermediates in the synthesi of note-1,5. V many organic compounds. 7 v3. A 2,8-bis(alpha-i'uryl metal sulphomethvl) Obviously many modification and variations in cycloheunone. the processes and compositions described above i JACK '1. THURSTON. may be made without departing'from the spirit 1o cEfimFicATE' OF GORRECTION. Patent'No. 2, 7 ,152; .April 10, 191

JACK 1'. mission.

It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction as followst Page 2, sec- .ond column, line 50, for the word "sub1nitted" read --substituted-; page 5, first column, line 7, after "many" insert -.-other--; and' that the said Letters Patent shouldbe read with this correction thereinthat the same inlay conform to the record of the case in the Patent Office- Signed and sealed this 26th day of June, A. 1:. 1915.

. Leslie Frazer (Seal) Acting" Commissioner of Patents. 

